Fungicidal and mite ovicidal substituted 2-aminobenzimidazoles



United States Patent Office 3,541,213 Patented Nov. 17, 1970 US. Cl. 424-273 36 Claims ABSTRACT OF THE DISCLOSURE Substituted Z-aminobenzimidazoles of the following three formulas are useful as mite ovicides and fungicides. The compounds also have utility in that when they are added to sewage, they result in an increase in the rate of sewage decomposition. When added to soil, the compounds increase the rate whereby the nitrogen present in fertilizers is converted into usable plant food. The compounds also possess activity against the helminth parasites of warm blooded animals.

FormulaI t X H C::N=CA

where one Q is Q t 1 -Qr where one Q is SZ and X, Z, Q and the other Q are as defined hereinafter. An exemplary species of this general class is the compound: l-(trichloromethylthio)-2- benzimidazolecarbamic acid, methyl ester.

Formula III where X, Q and Q are as defined hereinafter. Q includes such groups as hydrogen, alkoxycarbonyl, acyl, and alkyl. An examplary species of the general class is the compound: 1-methylcarbonyl-Z-benzimidazolecarbamic acid, methyl ester.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of my copending application Ser. No. 629,900, filed Apr. 11, 1967, now abandoned, which application is a continuation-inpart of my copending application Ser. No. 548,034, filed May 6, 1966, now abandoned.

BACKGROUND OF THE INVENTION This invention relates to substituted Z-aminobenzimidazoles and to methods of using these compounds to prevent or mitigate damage to plants and inanimate organic materials by fungi and mites.

The survival of man has for a long time been dependent in a large measure upon his ability to protect from the various agents of destruction, plants and their products which satisfy his basic needs. With the rapidly increasing population of the world it becomes imperative that there be continuing great improvements in the efficiency of the materials and the methods employed to provide this protection. These improvements can be in the form of effective control of more kinds of pests or in the form of requiring less material or work. The materials and methods of this invention represent marked advances in both of these possible areas of improvement, as will be explained more fully.

I have discovered that application of the compounds of this invention by the methods of this invention, surprisingly, entirely precludes or reduces damage to plants and inanimate organic materials due to both fungi and mites. Fungus mycelia are killed or prevented from developing further by the presence of one or more of the compounds, i.e., the compounds are fungicidal or fungistatic. The compounds further prevent mite populations from expanding or reduce them to a low level or even eliminate them by preventing the normal hatching of their eggs, i.e., the compounds are mite ovicides.

The compounds and methods of this invention also make possible the control of damage by both fungi and mites with an amazingly small amount of chemical and with surprisingly little etfort. These advantages are due in large measure to the fact that the compounds when properly applied, can enter and move about in plants. This means that an entire plant can be protected from mites and fungi with a simple application of the chemical to only a part of it, i.e., the compounds are systemic. Further, if the compounds are applied after a disease causing fungus is already established within a plant, they can enter the tissues and eradicate the infection, i.e., the compounds are curative. Thus, the need for applications prior to the actual incidence of the disease i eliminated under many circumstances.

SUMMARY OF THE INVENTION It has been found that the above outstanding fungicidal and mite ovicidal activity can be obtained by applying to the locus of mite or fungus infestation, the compounds represented by the following three formulas:

Formula I wherein X is hydrogen, halogen, alkyl of 1 through 4 carbon atoms, nitro, or alkoxy of 1 through 4 carbon atoms; A is R or R Its or CDER with the proviso that the total carbon content of R R and Q shall not exceed 18 carbon atoms;

R is methyl or ethyl;

R is alkyl of 1 through 4 carbon atoms or allyl;

R is hydrogen, alkyl of 1 through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms or alkynyl of 3 through 6 carbon atoms;

R is hydrogen; alkyl of 1 through 18 carbon atoms; alkyl of 1 through 18 carbon atoms substituted with halogen, alkoxy of 1 through 4 carbon atoms, or alkoxycarbonyl of 2 through 4 carbon atoms; alkenyl of 3 through 18 carbon atoms; alkenyl of 3 through 18 carbon atoms substituted with halogen, alkoxy of 1 through 4 carbon atoms, or alkoxycarbonyl of 2 through 4 carbon atoms; alkynyl of 3 through 18 carbon atoms; alkynyl of 3 through 18 carbon atoms substituted with halogen, alkoxy of 1 through 4 carbon atoms, or alkoxycarbonyl of 2 through 4 carbon atoms; cycloalkyl of 3 through carbon atoms; cycloalkyl of 3 through 10 carbon atoms substituted with methyl, methoxy, or chlorine; cycloalkenyl of 4 through 8 carbon atoms; cycloalkenyl of 4 through 8 carbon atoms substituted with methyl, methoxy, or chlorine; bicycloalkyl of 7 through 10 carbon atoms; bicycloalkenyl of 7 through 10 carbon atoms; (cycloalkyl)alkyl of 4 through 9 carbon atoms; (cyc1oalkyl)alkyl of 4 through 9 carbon atoms substituted with methyl, methoxy, or chlorine; (cycloalkenyUalkyl of 5 through 9 carbon atoms; aralkyl of 5 through 8 carbon atoms; aralkyl of 5 through 8 carbon atoms substituted with al kyl of 1 through 4 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, fluoroalkyl of I through 4 carbon atoms, alkoxy of 1 through 4 carbon atoms, halogen, cyano, alkoxycarbonyl of 2 through 3 carbon atoms, alkylsulfonyl of 1 through 4 carbon atoms, or nitro; phenyl; phenyl substituted with alkyl of 1 through 4 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, fluoroalkyl of 1 through 4 carbon atoms, itlkoxy of 1 through 4 carbon atoms, halogen, cyano, allroxycarbonyl of 2 through 3 carbon atoms, alkylsulfonyl of 1 through 4 carbon atoms, or nitro; alkylsulfonyl of 1 through 18 carbon atoms; phenylsulfonyl; phenylsulfonyl substituted with alkyl of 1 through 4 carbon atoms, alkoxy of 1 through 4 carbon atoms, halogen, cyano, alkoxycarbonyl of 2 through 3 carbon atoms, or nitro; acyl of 1 through 18 carbon atoms; acyl of 1 through 18 carbon atoms substituted with halogen or alkoxy of 1 through 4 carbon atoms; aroyl of 6 through 10 carbon atoms; or aroyl of 6 through 10 carbon atoms substituted with alkyl of 1 through 4 carbon atoms, halogen, nitro, alkylsulfonyl of 1 through 4 carbon atoms or alltoxy of 1 through 4 carbon atoms; provided that when R and R are both substituents on the same nitrogen, they can be taken together to be (CH where n is 2 to 8 2)2- 2)Z R is hydrogen; alkyl of 1 through 12 carbon atoms; alkyl of 1 through 12 carbon atoms substituted with hydroxy, -CR cyano, acetoxy, chlorine or fluorine; alkynyl of 2 through 10 carbon atoms; alkenyl of 2 through 10 carbon atoms; cycloalkyl of 3 through 8 carbon atoms; chlorine; alkoxycarbonyl of 2 through 5 carbons; or aryl of the type Q R is alkyl of 1 through 12 carbons, alkenyl of 3 through 10 carbons, alkynyl of 3 through 10' carbons, cycloalkyl of 3 through 8 carbons, (cycloalkyUalkyl of 7 through 10 carbons, phenyl or benzyl;

R is hydrogen, alkyl of 1 through 3 carbons or cycloalkyl of 3 through 4 carbons; and

D, E and W are oxygen or sulfur. Preferred within Formula I because of their greater stability are the compounds of the following formula:

wherein R is methyl, ethyl, isopropyl or sec-butyl;

R is hydrogen, alkyl of 1 through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms or alkynyl of 3 through 6 carbon atoms;

R is hydrogen; alkyl of 1 through 12 carbon atoms; alkyl of 1 through 12 carbon atoms substituted with halogen, alkoxy of 1 through 4 carbon atoms, or alkoxycarbony] of 2 through 4 carbon atoms; alkenyl of 3 through 12 carbon atoms; alkyny] of 3 through 12 carbon atoms; cycloalkyl of 3 through 8 carbon atoms; cycloalkyl of 3 through 8 carbon atoms substituted with methyl, methoxy, or chlorine; cycloalkenyl of 4 through 8 carbon atoms; (cycloalkyl)alkyl of 4 through 9 carbon atoms; (cycloalkyl)alkyl of 4 through 9 carbon atoms substituted with methyl, methoxy, or chlorine; (cycloalkeny1)alkyl of 5 through 9 carbon atoms; aralkyl of. 5 through 8 carbon atoms; aralkyl of 5 through 8 carbon atoms substituted with alkyl of 1 through 4 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, fiuoroalkyl of 1 through 4 carbon atoms, alkoxy of 1 through 4 carbon atoms, halogen, cyano, alkoxycarbonyl of 2 through 3 carbon atoms, alkylsulfonyl of 1 through 4 carbon atoms, or nitro; phenyl; phenyl substituted with alkyl of 1 through 4 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, fluoroalkyl of 1 through 4 carbon atoms, alkoxy of 1 through 4 carbon atoms, halogen, cyano, alkoxycarbonyl of 2 through 3 carbon atoms, alkylsulfony] of 1 through 4 carbon atoms, or nitro; alkylsulfonyl of 1 through 12 carbon atoms;

phenylsulfonyl; phenylsulfonyl substituted with alkyl of 1 through 4 carbon atoms, alkoxy of 1 through 4 carbon atoms, halogen, cyano, alkoxycarbonyl of 2 through 3 carbon atoms, or nitro; acyl of 1 through 12 carbon atoms; acyl of 1 through 12 carbon atoms substituted with halo gen or alkoxy of 1 through 4 carbon atoms; aroyl of 6 through 10 carbon atoms; or aroyl of 6 through 10 carbon atoms substituted with alkyl of 1 through 4 carbon atoms. halogen, nitro, alkylsulfonyl of 1 through 4 carbon atoms or alkoxy of 1 through 4 carbon atoms; provided that when R and R are both substituents on the same nitrogen, they can be taken together to be (CH where n is 2 to 8 or (CH O-(CH and provided that the total carbon content of R and R shall not exceed 12 carbons.

Preferred Within Formula I because of their greater pesticidal activity are the compounds of the following formula:

Formula 1B wherein R is methyl, ethyl, isopropyl or sec-butyl; and

R is alkyl of 1 through 12 carbon atoms; phenyl; phenyl substituted with methyl, ethyl, methoxy, ethoxy, nitro, CF CH SO or halogen; benzyl; benzyl substituted with methyl, nitro, methoxy, or halogen; (cycloa1kyl)alkyl of 7 through 8 carbon atoms; (cycloalkyl)alkyl of 7 through 8 carbon atoms substituted with methyl; cyclohexyl; or cyclohexyl substituted with methyl.

Preferred within Formula I on the basis of economics and ease of manufacture are the compounds of the following formula:

Formuln IC wherein R is methyl or ethyl and R is alkyl of 1 through 8 carbon atoms.

Most preferred within Formula I in view of highest activity are the following compounds:

1 butylcarbamoyl-2-benzimidazolecarhamic acid, methyl ester;

l-hexylcarbamoyl-Z-benzimidazolecarbamic acid, methyl ester;

1-octaylcarbamoyl-2-benzimidazolecarbamic acid, methyl ester; and

1-(p-methoxyphenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester.

It has not been entirely established whether the trisubstituted benzimidazoles of Formula I have structure (A) or structure (B) below:

For the pulpose of this description, all the trisubstituted compounds are named as the 1,2,3-trisubstituted benzimidazolines (structure (8)) with the understanding that the invention covers the corresponding pure l,N,N-tr1'- substituted positional isomers and isomeric mixtures thereof as they are likely to occur.

In a further aspect, the invention relates to the following novel compounds and their outstanding fungicidal and mite ovicidal activity.

Formula II where Q is -SZ; hydrogen, -CDER cyano;

t r C*N ;CRl Rs alkylsulfonyl of 1 to 6 carbon atoms;

W Wk

methyl; methyl substituted with CN, --COOR, or OR; alkenyl of 3 or 4 carbon atoms; propargyl; phenylsulfonyl; phenylsulfonyl substituted with halogen, methoxy, methyl or ethyl; benzylsulfonyl; or benzylsulfonyl substituted with halogen, methoxy, methyl or ethyl; provided that Q, cannot be hydrogen when Q is hydrogen, and further provided that the total carbon content of Q and Z cannot exceed 19 carbon atoms;

R is methyl or ethyl;

R is alkyl of 1 through 4 carbon atoms or allyl;

R is hydrogen, alkyl of 1 through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms or alkynyl of 3 through 6 carbon atoms;

R, is hydrogen; alkyl of 1 through 18 carbon atoms; alkyl of 1 through 18 carbon atoms substituted with halogen, alkoXy of 1 through 4 carbon atoms, or alkoxycarbonyl of 2 through 4 carbon atoms; alkenyl of 3 through 18 carbon atoms; alkynyl of 3 through 18 carbon atoms; alkenyl of 3 through 18 carbon atoms substituted with halogen, alkoxy of 1 through 4 carbon atoms, or alkoxycarbonyl of 2 through 4 carbon atoms; alkynyl of 3 through 18 carbon atoms substituted with halogen, alkoxy of 1 through 4 carbon atoms, or alkoxycarbonyl of 2 through 4 carbon atoms; cycloalkyl of 3 through 10 carbon atoms; cycloalkyl of 3 through 10 carbon atoms substituted with methyl, methoxy, or chlorine; cycloalkenyl of 4 through 8 carbon atoms; cycloalkenyl of 4 through 8 carbon atoms substituted with methyl, methoxy or chlorine; bicycloalkyl of 7 through 10 carbon atoms; bicycloalkenyl of 7 through 10 carbon atoms; (cycloalkyDalkyl of 4 through 9 carbon atoms; (cycloalkyl)alkyl of 4 through 9 carbon atoms substituted with methyl, methoxy, or chlorine; (cycloalkenyl)alkyl of 5 through 9 carbon atoms; aralkyl of 5 through 8 carbon atoms; phenyl; phenyl substituted with alkyl of 1 through 4 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, fluoroalkyl of 1 through 4 carbon atoms, alkoxy of 1 through 4 carbon atoms, halogen, cyano, alkoxycarbonyl of 2 through 3 carbon atoms, alkylsulfonyl of 1 through 4 carbon atoms, or nitro; aralkyl of 5 through 8 carbon atoms substituted with alkyl of 1 through 4 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, fiuororalkyl of 1 through 4 carbon atoms, alkoxy of 1 through 4 carbon atoms, halogen, cyano, alkoxycarbonyl of 2 through 3 carbon atoms, alkylsulfonyl of 1 through 4 carbon atoms, or nitro; alkylsulfonyl of 1 through 18 carbon atoms; phenylsulfonyl; phenylsulfonyl substituted with alkyl of 1 through 4 carbon atoms, alkoxy of 1 through 4 carbon atoms, halogen, cyano, alkoxycarbonyl of 2 through 3 carbon atoms, or nitro; acyl of 1 through 18 carbon atoms; acyl of 1 through 18 carbon atoms substituted with halogen or alkoxy of 1 through 4 carbon atoms; aroyl of 6 through 10 carbon atoms; or aroyl of 6 through 10 carbon atoms substituted with alkyl of 1 through 4 carbon atoms, halogen, nitro, alkylsulfonyl of 1 through 4 carbon atoms or alkoxy of 1 through 4 carbon atoms; provided that when R and R are both substituents on the same nitrogen, they can be taken together to be -(CH where n is 2 to 8, 2)-- 2)z;

R is hydrogen: alkyl of 1 through 12 carbon atoms; alkyl of 1 through 12 carbon atoms substituted with chlorine, fluorine, cyano, hydroxy, acetoxy or OR chlorine; cycloalkyl of 3 through 8 carbon atoms; alkenyl of 2 through 10 carbon atoms; alkynyl of 2 through 10 carbon atoms; aryl of the formula:

or alkoxycarbonyl of 2 to carbon atoms;

R is alkyl of 1 through 12 carbon atoms, alkenyl of 3 through carbon atoms, alkynyl of 3 through 10 (cycloalkyl)alkyl of 7 through 10 carbon atoms, phenyl or benzyl; cycloalkyl of 3 through 8 carbon atoms;

R is hydrogen, alkyl of 1 through 3 carbon atoms or cycloalkyl of 3 through 4 carbon atoms; and

D, E and W are oxygen or sulfur.

Preferred within Formula II because of their greater stability are compounds of the following formula:

Formula II A R is methyl, ethyl, isopropyl or sec.-butyl; and

Z is alkyl of 1 through 3 carbon atoms; alkyl of 1 through 3 carbon atoms substituted with chlorine; phenyl; phenyl substituted with methyl, nitro, or chlorine; benxyl; or benzyl substituted with methyl, nitro or chlorine.

Preferred within Formula II on the basis of economics and ease of manufacture are compounds of the following formula:

Formula II B wherein R is methyl, ethyl or isopropyl; and

Z" is trichloromethyl or 2,4-dinitrophenyl.

Most preferred within Formula II are the following compounds:

stituted benzimidazoles of Formula II has structure (A) or structure (B) below.

For the purpose of this description all the trisubstituted compounds are named as the 1,2,3-benzimidazolines (structure B) with the understanding that the invention covers the corresponding pure 1,N,N-trisubstituted isomers and isomeric mixtures as they are likely to occur.

In yet another aspect, the invention relates to the outstanding fungicidal and mite ovicidal activity obtained by applying to the locus of mite or fungus infestation, the compounds represented by the following formula:

Formula III wherein X is hydrogen, halogen, alkyl of 1 through 4 carbon atoms, nitro, or alkoxy or 1 through 4 carbons;

Q is hydrogen, CDER or The other Qs are the same or different and are hydro gen; methyl; methyl substituted or ()R, CN or COOR; alkenyl of 3 through 4 carbon atoms; propargyl;

9 cyano; alkylsulfonyl of 1 through 6 carbon atoms; phenylsulfonyl; benzylsulfonyl; CDER or trichloromethylsulfonyl; provided that when one Q and Q are each either hydrogen or COOR the other Q cannot be hydrogen or COOR and further provided that the total number of carbon atoms for the two Qs cannot exceed 14 carbon atoms;

R is methyl or ethyl;

R is alkyl of 1 through 4 carbon atoms or allyl;

R is alkyl of 1 through 6 carbon atoms, alkenyl of 1 through 6 carbon atoms or alkynyl of 1 through 6 carbon atoms;

R, is hydrogen; alkyl of 1 through 12 carbon atoms; alkyl of 1 through 12 carbon atoms substituted with bydroxy, OR acetoxy, chlorine, fluorine or cyano; chlorine; alkenyl of 2 through carbon atoms; alkynyl of 2 through 10 carbon atoms; cycloalkyl of 3 through 8 carbon atoms; aryl of the formula:

or alkoxycarbonyl of 2 through 5 carbon atoms;

R is alkyl of 1 through 12 carbon atoms; alkyl of 1 through 12 carbon atoms substituted with cyano, hydroxy, 0R, chlorine or bromine; alkenyl of 3 through 10 carbon atoms; alkynyl of 3 through 10 carbon atoms; cycloalkyl of 3 through 8 carbon atoms; (cycloalkyl)alky1 of 7 through 10 carbon atoms; (cycloalkyl)alkyl of 7 through .10 carbon atoms substituted with methyl, methoxy or chlorine;

R, is hydrogen, alkyl of 1 through 3 carbon atoms, or cycloalkyl of 3 through 4 carbon atoms; and

D, E and W are oxygen or sulfur.

Preferred within Formula III on the basis of their stability are the compounds of the following formula:

FORMULA IlIA wherein Q, is COOR or o [I -CRe' Q is hydrogen; methyl; methyl substituted with cyano, OR or COOR; cyano; CDER cycloalkyl of 3 through 8 carbon atoms; chlorine; aryl of the type:

or alkoxycarbonyl of 2 to 5 carbons;

X is hydrogen, halogen, alkyl of 1 through 4 carbon atoms, nitro, or alkoxy of 1 through 4 carbon atoms;

R is alkyl of 1 through 12 carbon atoms; alkyl of 1 through 12 carbon atoms substituted with cyano, hy droxy, OR, chlorine or bromine; alkenyl of 3 through 10 carbon atoms; alkynyl of 3 through 10 carbon atoms; cycloalkyl of 3 through 8 carbon atoms; (cycloalkyl)- alkyl of 7 through 10 carbon atoms; (cycloalkyl)alkyl of 7 through 10 carbon atoms substituted with methyl, methoxy or chlorine;

R is hydrogen, alkyl of 1 through 3 carbon atoms or cycloalkyl of 3 through 4 carbon atoms; and

D, E and W are oxygen or sulfur.

Preferred within Formula 111 on the basis of economics and ease of manufacture are the compounds of the following formula:

FORMULA IIlB R is methyl, ethyl, isopropyl or sec-butyl;

R is hydrogen; alkyl of 1 through 12 carbon atoms; alkyl of 1 through 12 carbon atoms substituted with cyano, hydroxy, methoxy, ethoxy, acetoxy, chlorine, or fluorine; chlorine; alkenyl of 2 through 10 carbon atoms; alkynyl of 2 through 10 carbon atoms; cycloalkyl of 3 through 8 carbon atoms; alkoxy-carbonyl of 2 through 5 carbon atoms and aryl of the formula:

and

R is alkyl of 1 through 3 carbon atoms or cycloalkyl of 3 through 4 carbon atoms.

Preferred within Formula III on the basis of their high pesticidal activity are the compounds of the following formula:

FORMULA IlIC wherein R is methyl or ethyl; and

R is alkyl of 1 through 4 carbons, cycloalkyl of 3 through 4 carbons, methoxycarbonyl, or ethoxycarbonyl.

Most preferred within Formula 111 are the following compounds:

l-acetyl-2-benzimidazolecarbamic acid, methyl ester I-propionyl-2-benzimidazolecarbamic acid, methyl ester 1 ethoxyoxyalyl Z-benzimidazolecarbamic acid, methyl ester 1 methoxyoxalyl 2-benzimidazolecarbamic acid, methyl ester DETAILED DESCRIPTION OF THE INVENTION The compounds of Formula I can be prepared by a number of routes. For example, the l-carbamoyl substituted 2-benzimidazolecarbamates can be prepared by reacting 2-benzimidazolecarbamates with isocyanates in accordance with the following reaction:

In this scheme, X and R are described in Formula I, and R is R or R as also described in Formula I.

The reaction as set forth in (1) above can be carried out in different inert solvents such as chloroform, carbon tetrachloride, methylene chloride, benzene, or cycylohexane. Mixtures of these solvents can also be used. The reaction can also be carried out without solvent by combining the two reactants in a closed system and subjecting them to shear or impact force, e.g., by use of a mix muller.

The reaction temperature, in general, is not critical and can be anywhere in between the freezing point and the boiling point of the reaction mixture, provided this boiling point is below the temperature at which reactants and products decompose. Ambient temperature is preferred.

The 1-carbamoyl-2-benzimidazolecarbamates can also be prepared by first preparing the corresponding l-chlorocarbonyl-Z-benzimidazolecarbamate from 2-benzimidzolecarbamate, phosgene and an acid acceptor, then reacting this 1 chlorocarbonyl 2- benzimidazolecarbamate with ammonia or substituted amines in accordance with the following sequence of reactions.

N l 11 Base 0 ll om X c II CWNIICOR1+ 2HN ll/ 7' X N Ra (n) R2 C-*NI'I-0-01h+ M11101 In In these schemes, X, R R and R are as described as in Formula I.

The reactions set forth in (2) and (3) can be carried out in solvents such as acetone, tetrahydrofuran, chloroform, methylenechloride, benzene, cyclohexane and carbon tetrachloride. Mixtures of these solvents can also be used.

Suitable bases are sodium hydroxide, sodium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, trimethylamine, tricthylamine, pyridine, and many others. These bases may be used either as such or in the form of a solution in a suitable solvent.

The reaction temperature is in general not critical, and as mentioned for reaction (1) can be anywhere in between the freezing point and the boiling point of the reaction mixture, provided this boiling point is below the temperature at which reactants and products decompose. Room temperature is generally most convenient and thus preferred.

The I,3-biscarbamoylsubstituted A -2-benzimidazolinecarbamates can be prepared by reacting Z-benzimidazolecarbamates with two equivalents of an isocyanate in accordance with the following reaction.

C NCORI 2R7NCO ii (|3NUR1 X N C=NCOR N Ali-NH:

In this scheme X, R and R and the reaction conditions are the same as described for reaction (1).

13 14 The l-carbamoyl substituted-3-carbamoyl substituted A -2-benzimidazolinecarbamates can be prepared by reacting l carbamoyl substituted 2 benzimidazolecarbai i-N mates with isocyanates in accordance with the following X reaction. 5

C==N(u1 o R o Q In this scheme, X, R R R and Q are as described in Formula I.

The reaction conditions for reaction (6) are similar x to those described for reaction (1) above.

The 2 imino 3-carbamoyl substituted-l-benzimidazolines used in reaction (6) can be prepared by reacting the R=NCO Z-imino-l-benzimidazolines with isocyanates in accord- 0 ance with the following reaction. I? H E /R: X

N\ R: (I; (I).

X X C=NC0R1 N (l C=NH 119100 cram N {\L-NIIR: N N

l H (|%NHR;

In this scheme, X, Q and R are as described as in Formula I and R is R or R; as described in Formula I. The reaction conditions for reaction (7) are the same as those for reaction (1).

The following examples illustrate the preparation of In this scheme and R3 am as described in the compounds of Formula I. The amounts are given in Formula I.

The reaction conditions for reaction (5) are the same terms of P s by weight unless otherwise specified. as those for reaction (1) above.

The l-carbamoyl substituted-3-substituted-A -Z-benZ- EXAMPLE 1 irnidazolinecarbamates can be prepared by reacting 1- f th b t 1 b m substituted carbamoyl-3-benzimidazolines with electrogg g gf g g gg sg g 0y) philic reagents (QW) such as alkyl chloroformates in accordance with the following reaction. To a slurry of 19.1 parts of methyl-2-benzimidazolecarbamate and 600 parts of chloroform are added 9.9

parts of n-butylisocyanate. The reaction is stirred at room temperature until a clear solution is present or until only a small amount of solid is present.

Any solids present are removed by filtration. The

solvent is removed from the filtrate under reduced pressure and essentially pure methyl 1-(butylcarbarnoyl)-2- benzrmidazolecarbamate 1s obtalned by triturating the re- 0 maining white solid with hexane and collecting the (ii-N product by filtration. X L Mum The following compounds are prepared in accordance O Nagco with the procedure set forth above by replacing c=NH+01g0m f n-butylisocyanate with the indicated isocyanate. The Refill! table shows not only the relative proportlons of the indicated isocyanates needed for 19.1 parts by weight of methyl-2-benzimidazolecarbamate but also the product obtained.

17 tained by triturating the residue with hexane and collecting the product by filtration.

To a solution of 12.7 parts of methyl l-chlorocarbonyl- Z-benzimidazolecarbamate and 300 parts of chloroform is slowly added 1.7 parts of ammonia. Any solids present are removed by filtration, and the filtrate is washed with water. The chloroform layer is dried and the solvent is removed under reduced pressure. Essentially pure methyl l-carbamoyl-2-benzimidazolecarbamate is obtained by triturating the remaining white solid with hexane and collecting the product by filtration.

The following compounds can be prepared in accordance with the above procedure by replacing the 12.7 parts of the appropriate 1-chlorocarbonyl-2-benzimidazbamate and the 1.7 parts of ammonia with equivalent parts of the appropriate 1-chlorocarbonyl-Z-benzimidazolecarbamic acid ester and the properly substituted amines necessary to prepare each named product.

Product methyl 1- N,N-dimethylcarbamoyl -2- benzimidazolecarbamate methyl 1-(N,N-dipropylcarbamoyl)-2- benzimidazolecarbamate methyl l- N,N-diethylcarbamoyl -2- benzimidazolecarbamate methyl l-(N,N-dibutylcarbamoyl)-2- benzimidazolecarbamate methyl 1-(N,N-dihexylcarbamoyl)-2- benzimidazolecarbamate methyl 1-(N-methyl-N-octylcarbamoyl)-2- benzimidazolecarbamate methyl 1-(N-dodeeyl-N-methylcarbamoyl)-2- benzimidazolecarbamate methyl 1-(N-ethyl-N-methylcarbamoyl)-2- benzimidazolecarbamate methyl l- N-hexyl-N-methylcarbamoyl -2- benzimidazolecarbamate methyl 1-(N-butyl-N-ethylcarbamoyl)-2- benzimidazolecarbamate methyl l-(piperidinocarbonyl)-2- benzimidazolecarbamate ethyl l-(N,N-dimethylcarbamoyl)2- benzimidazolecarbamate propyl l-(N,N-dimethylcarbamoyl)-2- benzimidazolecarbamate butyl l-(N,N-dimethylcarbamoyl)-2- benzimidazolecarbamate allyl 1-(N,N-dimethylcarbamoyl)-2- benzimidazolecarbamate ethyl l-(pipen'dinocarbonyD-Z- benzimidazolecarbamate methyl l-(pyrrolidinocarbonyl)-2- benzimidazolecarbamate methyl 1-(N-cyclohexyl-N-ethylcarbamoyl)-2- benzimidazolecarbamate methyl 1- [N-methyl-N- ptoluoyl carbamoyl -2- benzimidazole-carbamate isopropyl l morpholinocarbonyl -2- benzimidazolecarbamate ethyl l-(N-butyl-N-methylcarbamoyl)-2- benzimidazolecarbamate ethyl 1-(N-cyelohexyl-N-ethylcarbamoyl)-2- benzimidazolecarbamate isopropyl l- (N-butyl-N-methylcarbamoyl -2- benzimidazolecarbamate isopropyl 1-(N-hexyl-N-methylcarbamoyl)-2- benzirnidazolecarbamate isopropyl l-[N-methyl-N-(p-tolyl)carbamoyl1-2- benzimidazolecarbamate ethyl l- [N-ethyl-N- p-tolyl carbamoyl] -2- benzimidazolecarbamate isopropyl 1-(N-cyclohexyl-N-methylcarbamoyl)-2- benzimidazolecarbamate propyl l-(N-butyl-N-methylcarbamoyl)-2- benzimidazolecarbamate propyl 1- [N-methyl-N- p-toluoyl carbamoyl] -2- benzimidazolecarbamate ethyl l-carbamoyl-2-benzimidazolecarbamate isopropyl 1-carbamoyl-Z-benzimidazolecarbamate propyl 1-carbamoyl-2-benzimidazolecarbamate butyl l-carbamoyl-Z-benzimidazolecarbamate methyl l-( l-aziridinyloarbonyl)-2- benzimidazolecarbamate methyl l- (octahydrolH-azoninl-ylcarbonyl) -2- benzimidazolecarbamate methyl l-(N,N-diallylcarbamoyl)-2- benzimidazolecarbamate methyl 1-(N,N-dipropropargylcarbamoyl)-2- benzimidazolecarbamate methyl l-(N,N-dihex-2-enylcarbamoyl)-2- benzimidazolecarbamate methyl l-(N,N-dibut-2-enylcarbamoyl)-2- benzimidazolecarbamate methyl 1-(N-allyl-N-methylcarbamoyl)-2- benzimidazolecarbamate methyl 1-(N-propargyl-N-methylcarbamoyl)-2- benzimidazolecarbamate methyl 1- N-hex-Z-vinyl-N-methylcarbamoyl) -2- benzimidazolecarbamate EXAMPLE 3 Preparation of methyl 1,3-bis(methylcarbamoyl)-A Z-benzimidazoleoarbamate To a slurry of 9.6 parts of methyl-2-benzimidazolecarbamate and 300 parts of chloroform are added 8.6 parts of methylisocyanate. The reaction is stirred at room temperature until a clear solution is present, or until a constant amount of solids are present. Any solids present are removed by filtration. The solvent is removed from the filtrate under reduced pressure, and essentiall pure methyl l,3-bis(methylcarbamoyl)-A -2-benzimidazolinecarbamate is obtained by triturating the remaining solid with hexane and collecting the product by filtration.

The following compounds of Formula I are prepared in accordance with the preceding procedure by replacing the 9.6 parts of methyl-Z-benzimidazolecarbamate and 8.6 parts of methylisocyanate with the equivalent parts of the Z-benzimidazolecarbamic acid ester and isocyanate necessary to prepare each named product.

Product methyl l,3-bis(butylcarbamoyl)-A -2- benzimidazolinecarbamate methyl l,3-bis(ethylcarbamoyl)-A -2- benzimidazolinecarbamate methyl 1 ,3-bis propylcarbamoyl -A -2- benzimidazolinecarbamate methyl l,3-his(pentylcarbamoyl)-A -2- benzimidazolinecarbamate methyl l,3-bis(hexylcarbamoyl)-A -2- benzimidazolinecarbamate methyl 1,3-bis(OctyIcarbamoyD-A -Z- benzimidazolinecarbamate ethyl l,3-bis(butylcarbam0yl)-A -2- benzimidazolinccarbamate methyl 1,3-bis(benzy1carbamoyl)-A -2- benzimidazolinecarbamate methyl 1,3-bis[ (p-tolyl) carbamoyl] -A -2- benzimidazolinecarbamate methyl 1,3-bis (p-chlorophenyl carbamoyl] A -2-benzimidazolinecarbamate methyl 1,3-bis (p-methoxyphenyl carbamoyl] A -2-benzimidazolinecarbamate methyl 1,3-bis[ (p-methoxycarbonylphenyl -carbamoyl] -A -2-benzimidazo1inecarbamate isopropyl l,3-bis(butylcarbamoyl) A -2- benzimidazolinecarbamate methyl I,3-bis(ethoxycarbonylmethylcarbamoyl)- A -2-benzimidazolinecarbarnate ester and isocyanate necessary to prepare each named product.

methyl 1,3-bis(methoxypropylcarbamoyl)-A Product 2-benzimidazolinecarbamate ethyl l3 bis(methylcarbamoyn A2,N 2 ethyl l-(buty]carbamoyl)-I i-(methyl-A -Z-benZmItdazbenzimidazolinecarbamate 5 Olmecarbamate ethyl l,3 bis(propylcarbamoyn A2,N 2 ethyl l-(hexylcarbamoyl)-3-(allyl)-A -2-benzimidazolinecarbamate benzimidazolinecarbamate ethyl 1,3-bis(ethoxycarbonylcarbamoyl)A -2- benzimidazolinecarbamate isopropyl l-( butylcarbamoyl -3-(ethoxycarbonylmethylcarbamoyl A -Z-benZimidazolinecarbamate sec butyl 3 bi h 1 b 1 g,1q 2 isopropyl l-(ethylcarbamoyl)-3-(hexylcarbamoyl)- benzimidazolinecarbamate A -2-benz|m1dazolmecarbamate sec-butyl 1,3-biS(bUtYICaIbarnOyU-A N-Z- methyl 1 (methoxypropylcarbamoyl)-3-(methylcarbambenzimida olineearbamat oy] -A -2-benzimidazolinecarbam ate EXAMPLE 4 ethyl l-(ethylcarbamoyl)-3-hexylcarbamoyl)A -2- benzimidazolinecarbamate Preparation of gy 9 y y sec-butyl 1-(methy1carbamoy1)-3-l(p loluoyl)- (methylcarbamoyD-A -2 benzimldazohnecarbamate b l A2,N 2 b i id li -b To a solution of 12.4 parts of methyl l-(methyl-carisobutyl l-(cyclohexylcarbamoyl)-3-ethoxycarbonylbamoyl)-2-benzimidazolecarbamate and 300 parts of methylcarbamoyl)-A -2-benzimidaz0linecarbamate chloroform are added 5.0 parts of butylisocyanate. The ethyl l-(methylcarbamoyl)-3-{(p-toIuoyUcarbamoyljreaction is stirred at room temperature until a clear solu- 12.b i id [i b 52%;:stdz ztzezesiz ieatzr :35 2:1 5:62: N -gg y r A enzimi azo inecarbamate The solvent is removed from the filtrate under reduced 25 isopropyl l (methylcarbamoyl) s [(p w1u0yl) pressure, and essentially pure methyl l-(butylcarbamoyl) carbamoylr]AlKLbenZimidazolinecarbamate 3-(methylcarbamoyl)A -Z-benzimidazolinecarbamate is 1 obtained by triturating the remaining solid with hexane P ig gi g 3'(tcyclohexylcarbamoyn and collecting the product by filtration. henzllml azil) mecar ama e I The following compounds are prepared in accordance l'(cyc ol?exy cflrbamoyl)'3'(hexylcdrbamoyl)' with the above procedure by replacing the butylisocyanate A 'z'banzlmldazolmecarbamate with the relative proportions of the indicated isocyanate methyl 1'(but YlC arban 103/1)'3'[(p'toluoyncarbamoyn needed for 12.4 parts of methyl l-(methylcarbamoylJ-Z- lzN'z-benllmldazolmecalbamate benzimidazolecarbamate. The product obtained is also yl l-( utylcarbamoyl)-3-(hexylcarbamoyl)-A -2- given. 3 benzimidazolinecarbamate Isocyannte lartshywt. Name Product 4.3 Propylisocyanate.-. Methyl1-tmethylcarbamoylyls- (propylcarhamoyD-N- -2- benzimidazolineearhaluate.

[3.4 llcxylisocyauate Methyl 1(hexylcarbamoyl)-3- (rncthylcarbamoyl)A -2- benziznirlazolinccarlmmate.

(L3 Cyclohcxylisocyanutc Methyl1-(eyclohexylcarhaimuyl)-3- (methylcarhnmoyl)A bcnzirnidazolinecarbamate.

7.0 4-methylcyelohcxylisocyauatc. Methyl l-(metliy carbamoyD-3- i(4-methylcyclohcxi;l)cnrbamoyfl- A -2-benzimidazo iut'carbamatu.

6.7 Bcuzylisocyanutc Methyl 1-(bcnzylearbamoyD-El-(mr-thyh carbamoyD-M- -24 euzimidazolinecarhaniate.

6.0 lhcnylisocyanate Methyl l-(methylcarhamoyU-3- (phenylcarbamoyUA -2- benzirnidazolinccarbamate.

6.7 p'loltloylisocyanatfi c. Methyl l-(methylearbamoyl)3- [(ptoluoyl)carba1noyl]-A -2- benzimidazolinccarhamate.

p-Chlorophcnyllsocyanate Methyl 1-[(p-chlorophenylmarbamoyll-li' (methylcarbamoyD-N- 2-benzimith azolinccurbamatc.

7,5 .t p-Mcthoxyphenylisocyanatmu Methyl l up-methoxyphenyl)carharnoyl]- 3 tmethylearbamoyl)-A=- -2- benzimidazolinccarhamate.

7,2 p-Cyanophenylisocyanate.. Methyl l-I(peyanophenyl)carbamoyH-B- (methylcarbarnoybut-2benzin1idazolinecarbamate.

s p-(Ittvthoxycarbonyll- Methyl1-l(p-methoxycarbolrylphenyhcarbamoyl 'B-(methyIcarb-amOyDA iZ-benzlmt azoliuecarbamate.

p-Nitrophenylisocyanatc t. Methyl l-(Inethylearbamoyl)-3- [(p-nitrophenyl)carbamoylI-M' 2-benzimidazolinecarbamute.

M ethyl 1-(ethoxycarbonylmcthylcarbamoyll-$(methylemlmrnoyl)- A -2-benzimidazolinccarbamatla 5,3 m;oxy o ylisocyauatc.tno Methyl1-(methoxypmpylcarbamoyl)- bcuzlmidazoliiicearhmnate.

pht'nylisoeynnatu.

6.5 Ethoxycarbonyhncthylisoeyauate.

EXAMPLE 5 7 l-(substitutcd curbamoylt-2-ben21midzuoleczu'bunuc acid hzuuoyl)-2-benu1nldazolecurlmnmlu and EXAMPLE 6 Preparation of methyl l-(methylcarbamoyU-3- propionylA -Z-benZimidaZolinecarbamate To it solution of l2.4 parts of methyl l-(methylcnr-- parts of 21 chloroform are added 4.7 parts of propionyl chloride. After stirring at room temperature for 1 hour, 5.1 parts of triethylamine are added to the reaction. The reaction is stirred at room temperature for 2 hours, then washed with water and dried. The solvent is removed under re- Product methyl 2-(isopropoxycarbonylimino)-3-(butylcarbamoyl -1-benzirnidazolinecarboxylate methyl Z-(methoxycarbonylimino)-3-(butylcarbamoyl)- l-benzimidazolinecarboxylate lu rs nill u lhl- Cad p e Sure and ta re 1 (.met y methyl Z-(ethoxycarbonyhmmo)-3-butylcarbamoyl)- carbamoyl) 3 PTOPlOHYl-A -2-benzimidazoliecarbal-benzimidazohnecarboxylate mate 18 obtained by tuturatmg the remaining solld with methyl 2-(ethoxycarbonylimmo)-3-(hexylcarbamoyl)- hexane and collecting the product by filtration. 1b b I The following compounds are prepared in accordance enzlmldazo mecar oxy ate th b d b l th 1 10 l-(allyloxyacetylcarbamoyl)-3-carbamoyl-2-benzimidaze 5 i y acmgf B AP' ohnecarbamlc acid, methyl ester ChOIldtBIWII the re any: proportions o t e 1n lcate 1 (laumyl) 3 methylcarbamoyl z benzlmldazolme acid halide needed for 1...4 parts of methyl l-(methylcarbamlc acld, methyl ester carbamoyl)-2-benzlmidazolecarbamate or the equivalent 1 1 1 3- m 1 2 d i weight of a l-(substituted carbamoyl)-3-substituted-2- 15 b i acid, isopropyl ester immobenzimidazolme carbamate. The product obtained 1 (2- t 1) 3 th l b i-2-b i id li is also given. carbamic acid, methyl ester Acid halide Parts by weight Product 4.7l .4 Methyl chlorofurmate Methyl Z-(methoxycarbonyllmine) (methylcarbarnoyD-l-benzimidazollnecarboxylatc. 7.2 2-chlor0cthylchl0r0[0rmate (2-chloroethyl)2-(mcthoxy-carbonylimlno)'3-(methylcarbam0yl)-1-benzimldazollnecarboxylatc. 5.7 Chloroacctyl chloride Methyl l-(chloloacetyll-3-(rnethyl-carbmnoyl)-A -2-bcnzimidazolinc-carbamate. 4.5 llydroxyacctylchloride Methyl1-(hydroxyacetyl)-3-(methylcarbamoyD-A -2-benzlmidazolinecarhamate. 6.2 Acctoxyacctyl chloride Methyl l-(acet0xyacetyl)-3-)methylcarbanwyD-N- -Z-beiulmidazolinecarbamate. 5.) Cyanoaeetyl chloride Methyl 1-(cyanioacetyl)-3-(mcthylcarbamoyll-A -?rbcnzimidrtzolinccarbarnate. 7. Benzoyl chloride... Methyl l-(bcuzuyD-il(methyl-carbamoyh- M -243mistimidazolinecarbamatev 8.8 p-Uhlorobenzoyl chloride Methyl l-(p-chlorobenzoyl)-3-(mcthylcarbamoyl)-A -Zbenzlmidazolinecarbamate. 10.1 BA-dichlorohcnzoyl chloride... Methyl1-(3,4-dichlorobenzoyb- -(methylcarbamoyl)A -2-benzlmldazolinecarbarnatc. 7.8 p-Toluoyl chloride Methyl l-(p-toluoyl)-3-(methyl-carhamoyl)-A '2-benzimidazolinccarbamatc. 9.3 p-Nitrobcnzoyl chloride Methyl l-(rnrthylcarbamoyl)-3-(p-nitmbenzoylyA il-benzimidazolinecar-hamate. 8.6 p-Anisoyl chloride Methyl 1-(p-Bnis0yl)-3-(methyl-carbamoyl)-A -Z-benzimidazolinecarbamate. 5.6 Methyl chl0r0thlcll0rmate Methyl 2-(rncthoxycarhrmyllmino}-3- (methylcarbamoyD-thiol-benzimidazol'lnccarboxylatc. 4.7. w lllcthylchloroformate Methyl1-(methoxycarbonyl)3(methylcarbamoyU-A -2benzlmidaz0linecarbamate. 8.l Dimcthyl chlurothiophos- Methyl 1-(dimethoxyphoephinothioyl)-3- ir te. (mcthylcarlmrneyll A -2-benzimidazolinecarbamate. 5.5 Ethyl chloroformcte Ethyl 2-(mcth0xycarbonylimino)-3- (methylcarbamoyl)-l-benzirnidazcllnecarboxylate. 8.3 .4 Hexyl chlorolormatc Hcxyl 2-(methoxycarbonylimlno)-&

(methylcarbamoyl)-1-benzimidazolinecarboxylate. 4.6 Acryloyl chloride Methyl1-(mcthylcarbamoyl)-3r(acryloy])- A -2-benzimldazolinccarhamate. 10.0 Bromoacetylbromlde Methyl l-(bl'0n10acetyl)-3(methylcarbamo l)-A -2-benzimldazolinecarbamate. 3.0 Acctyl chloride Methyl l-(acctyl)-3-(mcthylcarbamoy1)- A -2-benzin1idazolinccarbamate. 4.7 Methyl chlorolorlnatc Methyl l-(f0rmyl)-3-(mcthylcarbamoyh- A -fl-benzimldazolinecarbamatc. 5.8 Mcthanesullonyl chloride... Methyl 1(n1ethancsullonyh-3-(mvth 1 carhamoylym- 2-benzimidazolinecarbamate. 5.2 Cyclopmpanecarboxylic acid Methyl 1-(cyclopropanecarbonyl)-3 chlcridc. (methylcarbamoyD-A -2-benzimidazolineearbamate. 7.3 Cyclohexenccarboxylic acid Methyl 1 (cyclohcxanccarbonyl)-3- chloride. (methylcarbamoyD-N' -2-benzimidazolinecarbarnate.

EXAMPLE 7 The following compounds are prepared in accordance with Example 6 by replacing the 12.4 parts of methyl l-(methylcarbarnoyl)-2benzimidazolecarbamate and 4.7 parts of propionyl chloride with the equivalent parts of the l-(substituted carbamoyl)-2-benzimidazolecarbamic acid ester, a Z-acylamidobenzimidazole or a 1,3-disubstituted 2-iminobenzimidazoline and electrophilic reagent necessary to prepare each named product.

l-(2-octynoyl)-3-methylcarbamoyl-Z-benzimidazolinecarbamic acid, methyl ester 1-(B-methyl-Z-nonenoyl)-3-ethylcarbamoyl-2-benzimidazolinecarbamic acid, methyl ester 1-(hutoxyoxalyl)-3-methylcarbamoyl-Z-benzimidazoline- Earbamic acid, methyl ester l-(hexylthiolcarbonyl)-3-butylcarbam0yl-2-benzimidazolinecarbarnic acid, methyl ester 1-(dodecyloxythiocarbonyl)-3-methylcarbamoyl-Z-benzimidazolinecarbamic acid, methyl ester 1- dodecylthiolcarbonyl -3-methylcarbamoyl-Z-benzimidazolinecarbamic acid, methyl ester 1- allylthiolca rbonyl -3-butylcarbamoyl-2-benzimidazolinecarbamic acid, methyl ester 1-(4-octenoxythiocarbonyl)-3-ethylcarbamoyl-2-benzimidazolinecarbamic acid, methyl ester 1-(propargylthiolcarbonyl)-3-methylcarbamoyl-Z-benzimidazolinecarbamic acid, methyl ester l-(3-octynoxythiocarbonyl)-3-methylcarbamoyl-2-benzimidazolinecarbamic acid, ethyl ester l-(cyclopropylmethylthiolcarbonyl)-3-methylcarbamoyl- Z-benzimidazolinecarbamic acid, methyl ester l-(cyclobutyloxythiocarbonyl)-3-ethylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester l-(cyclooctyloxythiocarbonyl)-3-methylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester l-(norbornylmethyloxythiocarbonyl)-3-methylcarbamoyl-2-benzimidazolinecarbamic acid, methyl ester ethyl 2- (methoxycarbonylimino) -3-(butylcarbamoyl )-1- benzimidazolinecarboxylate ethyl Z-(ethoxycarbonylimino)-3-(hexylcarbamoyl)-1- benzimidazolinecarboxylate ethyl 2- isopropoxycarbonylimino -3- (propylcarbarnoyl)-1-benzimidazolinecarboxylate isopropyl Z-(rnethoxycarbonylimino -3- butylcarbamoyl)-l-benzimidazolinecarboxylate isopropyl 2- ethoxycarbonylimino -3- (propylcarbamoyl)-I-benzimidazolinecarboxylate isopropyl 2-(isopropoxycarbonylimino)-3-(methylcarbamoyl 1 -benzimidazolinecarboxylate butyl 2-(ethoxycarbonylimino)-3-(butylcarbamoyl)-1- benzimidazolinecarboxylate cyanoethyl 2-(methoxycarbonylimino)-3-(carbamoyl)-lbenzimidazolinecarboxylate methyl 1- (butylcarbamoyl -3- (benzenesulfonyl -A -2- benzimidazolinecarbamate hydroxyethyl Z-(ethoxycarbonylimino -3- (hexylcarbamoyl)-l'benzimidazolinecarboxylate ethyl l-(butylcarbamoyl)-3-(chloroacetyl)-A -2- benzimidazolinecarbamate ethyl l-(hexylcarbamoyl)-3-(hydroxyacetyl)h -2- benzimidazolinecarbamate ethyl l-(acetoxyacetyl)-3-(cyclohexylcarbamoyl)-A -2- benzimidazolineearbamate ethyl l-(cyanoacetyl)-3-(hexylcarbamoyl)-A "-2-benzimidazolinecarbamate ethyl l(butylcarbamoyl)-3-(p-toluoyl)-A -2-benzimidazolinecarbamate ethyl 1- (cyclohexaneca rbonyl -3- propylcarbamoyl) A -2-benzimidazolinecarbamate ethyl Z-(ethoxycarbonylimino)-3-(butylcarbamoyl)- thio- 1 -b enzimidazolinecarb oxyl ate methyl 2-(methoxycarbonylirnino)-3-(methylcarbamoyl thiono-1-benzimidazolinecarboxylate methyl 2-(ethoxycarbonylimino)-3-(butylcarbamoy1)-1- benzimidazolinecarbodithioate ethyl l-(butylcarbamoyl)-3-(ethanesu]fonyl)-A -2- benzimidazolinecarbamate methyl l-(butylcarbamoyl)-3-cyano-A -2-benzimidazolinecarbamate ethyl l-(butylcarbamoyl)-3-(diethylphosphonyl)-A 2-benzimidazolinecarbamate methyl l-(butoxyacetyl)-3-(methylcarbamoyl)u -2- benzimidazolinecarbamate methyl l-(ethynylcarbonyl)-3-(methylcarbamoyl)- A -Z-benZimidazolinecarbamate methyl l-butylcarbamoyl-3-ethoxyoxalyl-2-benzimidazolinecarbamate secbutyl l-rnethylcarbamoyl-3-methoxyoxalyl-2- benzimidazolinecarbamate methyl l-butylcarbamoyl-3-methoxyoxalyl-Z-bcnzimiduzolinecarbamate 1-butylcarbamoyl-3-methoxyoxalyl-2-propionamidobenzimidazoline I-butylcarbamoyl-3-methoxy (thiocarbonyl )-2-pr0pionarnidobenzimidazoline All of the compounds of this example can also be prepared by refluxing an acetone mixture containing an alkylchloroformate or an acyl chloride with the properly 1,3- disubstituted-Z-iminobenzimidazoline and sodium bicarbonate. Exemplary of this reaction is the following preparation of methyl l-(butylcarbamoyl)-3-(methoxycarbonyl)-2-benzimidazolinecarbamate.

A total of 9.4 parts of methylchloroformate contained in 50 parts of acetone is added slowly to a slurry of 29 parts of methyl 1-butylcarbamoyl-2-imino-l-benzimidazolinecarboxylate, 8.4 parts of sodium bicarbonate and 350 parts of acetone at 25 C. The reaction is refluxed for 2 hours then cooled to 5 C.

A total of 300 parts of cold water is added to, the reaction medium followed by an extraction with chloroform solvent. The chloroform layer is removed, dried over anhydrous magnesium sulfate and stripped free of solvent under reduced pressure. An oil remained which turned solid when triturated in hexane.

The solid removed by filtration is essentially pure methyl l-(butylcarbamoyl)-3-(methoxycarbonyl)-2-benzimidazolinecarbamate.

EXAMPLE 8 The following compounds are prepared in accordance with Example 1 by replacing the 19.1 parts of methyl-2- benzirnidazolecarbamate and 9.9 parts of n-butylisocyanate with the equivalent parts of the properly substituted benzimidazole and isoeyanate necessary to prepare each named product.

Product ethyl 1-(rnethylcarbamoy1)-2-(S-iodobenzimidazolecarbamate) ethyl 1 (3-butoxypropylcarbamoyl)-2-benzimidazolecarbamate ethyl 1-(allylcarbamoyl)-2-benzimida2olecarbamate ethyl l-(isopropylcarbamoyl)-2-benzirnidazolecarbamate ethyl l-(butylcarbamoyl)-2-(5-fluorobenzimidazo1ecarbamate) ethyl l-(sec-butylcarbamoyl)-2-benzimidazolecarbamate ethyl 1-(8,9-dichloroheptadecylcarbamoyl)-2-benzirnidazolecarbamate ethyl l-(hexylcarbamoyl)-2-benzimidazolecarbamate ethyl l-(octylcarbamoyl)-2-benzimidazolecarbamate ethyl l-(dodecylcarbamoyl)-2-benzimidazolecarbamate ethyl 1- cyclohexylcarbamoyl) -2-benzimidazolecarbamate ethyl 1-[ (Z-methylcyclohexyl carbamoyl] -2-benzirnidazolecarbamate ethyl l-( (4 methylcyclohexyl)carbamoyl] -2-benzimidazolecarbamate ethyl l [(P toluoyl)carbamoyl]-2-benzimidazolecarbamate ethyl 1 [(o-chlorophenyl)carbamoyl]-2-benzimidazolecarbamate ethyl 1-[ (p-isopropylphenyl) carbamoyl] -2-benzimidazolecarbamate ethyl 1- (4-methoxycyclohexyl carbamoyl -2-benzimidazolecarbamate ethyl 1 (cyclopentylcarbamoyl)-2-benzimidazolecarbamate ethyl 1-( cyclooctylcarbamoyl -2-benzi1nidazolecarbamate ethyl l-(benzylcarbamoyl) -2-benzimidazolecarbamate ethyl 1 [(p-methylbenzyl)carbamoyl]-2-benzimidazolecarbamate ethyl 1 [(3,4 xylyl)carbamoyl]-2-benzimidazolecarbamate ethyl 1- (p-methoxyphenyl)carbamoyl] -2-benzimidazolecarbamate ethyl I-[ (ethoxycarbonyl methyl )carbamoyl |-2-benzimitlazolecarbamate methyl l-(undecenoylcarbamoyl)-2-benzimidaz0lecarbamate methyl l-(isopropylpropiolylcarbamoyl)-2-benzimidazolecarbamate methyl 1-(crotonylcarbamoyl)-2-benzimidazolecarbamate methyl 1-(3-hexenoylcarbamoyl)-2-benzimidazolecarbamate methyl l-(3-buter1oy1carbam0yl)-2-benzimidaz0lecarbamate methyl 1-(p-chlorobenzylcarbamoyl)-2-benzin1idaz0lecarbamate isopropy] 1-(p-nitrobenzylcarbamoyl)-2-benzimidazolecarbamate methyl 1-(p-methylbenzylcarbamoyl)-2-benzimidazolecarbamate methyl l-(o-nitrobenzylcarbamoyl)-2-benzimidazo1ecarbamate methyl 1-(p-methoxybenzylcarbamoyl)-2-benzimidazole carbamate methyl 1- 3 ,4-dimethylbenzylcarbamoyl -2-benzimidazolecarbamate ethyl l-(allyl)-3-(carbamoyl)-A -2-benzimidaz0linecarbamate methyl I-(Z-butenyl)-3-(meLhyICarbamOyU-AE Z- benzimidazolinecarbamate methyl I-(propargyl)-3-(methylcarbamoyl)A -2- benzimidazolinecarbamate methyl l-(8-decenylcarbamoyl)-2-benzimidazolecarbamate methyl I-(S-heptadecynylcarbamoyl)-2-benzimidaz0lecarbamate methyl 1- (propargylcarbamoyl) -2-benzimi'dazolecarbamate methyl 1-(ketostearoylcarbam0yl)-2-benzimidazo1ecarbamate methyl l-(8-heptadecenylcarbamoyl)-2-benzimidazolecarbamate methyl 1-(8-pentadecenylcarbamoyl)-2-benzimidazolecarbamate methyl 1-(3-hexenylcarbamoyl)-2- benzimidazolecarhamate methyl l-(cyclopropylmethylcarbamoyl)-2-benzimidazolecarbamate methyl l-(cyclopentylmethylcarhamoyl)-2-benzimidazolecarbamate methyl 1-(cyclohexylmethylcarbamoyl)-2-henzimidazolecarbamate methyl l-(norbornylmethylcarbamoyl)Q-benzimidazolecarbamate methyl 1-(cyclooctylmethylcarhamoyl)-2-benzimidazolecarbamate l- -methylcyclohex-2-enylcarbamoyl -2-benzimidazolecarbamic acid, methyl ester 1-(4-methoxycycl0hex-2-enylcarbamoyl)-2-henzimidazolecarbamic acid, methyl ester l-(4-chlorocyclohex-Z-enylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester l-(4-methylcyclopen-Z-enylcarbam0yl) 2-benzimidazolecarbamic acid, methyl ester 1-( l-tetrahydronaphthylcarbarnoyl) -2-benzimidaz0lecarbamic acid, methyl ester 1-(fenchylcarbarnoyl)-2-benzimidazolecarbamic acid,

methyl ester 1- (octahydrona phthylcarbamoyl) -2-benzimidazolecarbamic acid, methyl ester isopropyl l-(butylcarbamoyl)-5-butyl-2-benzimidaz0lecarbamate methyl l-(butylcarbamoyl)-5-chloro-2-benzimidazolecarbamate methyl l i(P-toluoyl)carbamoyl]-5-nitro-2-benzimidztzulecarhumate methyl l(hutylcurhumoyl l-5-mcthyI-Z-hciuimidumlccurb-amide methyl l-(hexylcarbamoyl)-5-meth0xy-2-benzimidaz0lecarbamate ethyl l-(butylcarbamoyl -5-bromo-2-benzimidazolecarbamate methyl l-(butylcarbamoyl)-5-butyl-2-benzimidazolecarbaniate methyl 1-(hexylcarbamoyl)-S-butoxy-2-benzimidazolecarbamate 1-(Z-methylcyclopentylmethylcarbamoyl)-2-benzimidazolecarbamic acid, ethyl ester 1- p-methoxycyclohexylmethylcarbamoyl -2-benzimidazolecarbamic ester, isopropyl ester 1-(m-methoxycyclohexylmethylcarbamoyl)-3-carbamoyl-Z-benzimidazolinecarbamic acid, methyl ester 1- (p-chlorocyclohexylmethylcarbamoyl) -2-berizimidazolecarbamic acid, methyl ester l-(2-phenethylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 1- (p-methylcyclohexylethylcarbamoyl -2-benzimidazolecarbamic acid, methyl ester methyl l-(methoxycarbonylmethyl)-3-(methylcarbamoyl)-A -2-benzimiclazolinecarbamate methyl 2-(propionylimino)-3-(butylcarbamoyl)-1- benzimidazolinecarboxylate 1- 4-butylbenzylcarbamoyl -2-benzimidazolecarbamic acid, methyl ester 1- p-trichlorobenzylcarbamoyl) -2-benzimidazolecarbamic acid, methyl ester 1- (o-fiuoromethylbenzylcarbamoyl) -2-benzimidazolecarbamic acid, methyl ester 1- (p-methoxybenzylcarbamoyl -2-benzimidazolecarbamic acid, methyl ester 1-(o-fluorobenzylcarbamoyl)-2-benzimidaz0lecarbamic acid, methyl ester 1- p-bromobenzylcarbamoyl -2-benzimidazolecarbamic acid, methyl ester 1-(o-nitrobenzylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 1- p-butylsulfonylbenzylcarbamoyl) -2-benzimidazolecarbamic acid, methyl ester 1- p-ethoxycarbonylbenzylcarbamoyl -2-benzimidaz0lecarbamic acid, methyl ester l-(p-chloromethylphenylcarbamoyl)-2-benzimidazolecarbamic acid, ethyl ester 1 m-trichloromethylphenylcarbamoyl -2-benzimidazolecarbamic acid, methyl ester l-(p-fluoromethylphenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 1- (p-trifluoromethylphenylcarbamoyl) -2-benzimidazo1ecarbamic acid, methyl ester 1-(p-methylsulfonylphenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 1-(p-butylsulfonylphenylcarbamoyl)-3-methylcarbamoyl- Z-benzimidazolinecarbamic acid 1- butoxyacetylcarbamoyl -2-benzimidazo1ecarbamic acid, methyl ester 1- (p-sec-butylbenzoylcarbarnoyl) -2-benzimidazolecarbamic acid, methyl ester 1- (p-methylsulfonylbenzoylcarbamoyl) -2-benzimidazolecarbamic acid, methyl ester 1-(p-butoxybenzoylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester l-(p-nitrophenylsulfonylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 1-(octadecylsulfonylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 1 (-p-methylphenylsulfonylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 1- (p-tert-butylphenylsulfonylcarb amoyl) -2-benzimidazolecarbamic acid, methyl ester I-(p-methoxyphenylsulfonylcarbamoyl)-2-henzimidazolccarbamic acid, methyl ester l p-butoxyphenylsulfonylcarbamoyl -2-benzimiduzolecarbamic acid, methyl ester l-(p=chlorophenylsulfonylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 1- p-bromophenylsulfonylcarbamoyl) -2-benzimidazolecarbamic acid, ethyl ester methyl 1-(4-methylcyclohexylcarbamoyl)-2-benzimidazolecarbamate methyl l-(4-chlorocyclohexylcarbamoyl)-2-benzimidazolecarbamate methyl l-(4-methoxycyclohexylcarbamoyl)-2-benzimidazolecarbamate methyl l-(2-cyclobutenylcarbamoyl)-2-benzimidazolecarbamate methyl l-(Z-cyclohexenylcarbamoyl)-2-benzimidazolecarbamate methyl 1-(2-cyclooctenylcarbamoyl)-2-benzimidazolecarbamate methyl 1-(1-cyclopentenylmethylcarbamoyl)-2-benzimidazolecarbarnate methyl l-(1-cyclooctenylmethylcarbamoyl)-2-benzimidazolecarbamate methyl 1-[p-(2-chloroethyl)carhaniloyl]-2-benzimidazolecarbamate methyl l-[p-(chloromethyl)benzylcarbamoyl1-2- benzimidazolecarbamate methyl 1-[p-(trifluoromethyl)benzylcarbamoyl]-2- benzimidazolecarbamate methyl 1-(p-cyanobenzylcarbamoyl)-2- benzimidazolecarbamate methyl 1-(pcarbomethoxybenzylcarbamoyl)-2- benzimidazolecarbamate methyl 1-(p-methylsulfonylbenzylcarbamoyl)-2- benzimidazolecarbamate methyl l-(p-cyanosulfanilamidocarbonyl)-2- benzimidazolecarbamate methyl 1-(p-carboethoxysulfanilamidocarbonyl)-2- benzimidazolecarbamate methyl 1-( l -naphthamidocarbonyl) -2- benzimidazolecarbamate methyl l-(p-butylsulfonylbenzamidocarbonyl)-2- benzimidazolecarhamate EXAMPLE 9 The following compounds are prepared in accordance with Example 6 by replacing the 12.4 parts of methyl 1- (methylcarbamoyl) 2 benzimidazolecarbamate and 4.7 parts of propionylchloride with the equivalent parts of the properly substituted benzimidazole and electrophilic reagent necessary to prepare each named product.

Product l-(cyanomethyl)-3-bntylcarbamoyl-2-benzimidazolinecarbamic acid, methyl ester l-(methoxymethyl) -3-rnethylcarbamoyl-2-henzimidazolinecarbamie acid, ethyl ester 1-(methoxycarbonylmethyl)-3-butylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1- (butoxycarbonylmethyl) -3 -methylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester l-(benzylsulfonyl)-3-ethylcarbamoyl-2-benzimidazolinecarbamic acid, methyl ester 1- (hexylsulfonyl -3-butylcarbamoyl-2-benzimidazolinecarbamic acid, methyl ester 1- (p-chlorophenylsulfonyl -3-methylca rbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1- (p-methoxyphenylsulfonyl) 3 -methylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1-(p-methylphenylsulfonyl)-3-hexylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1- (p ethylphenylsulfonyl )-3-methylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester methyl l-(butylcarbamoyl)-3-cyan0-A -2-benzimidazolinecarbamate methyl 1-(methoxycarbonyl)-3-dimethylcarbamoyl)- A -2-benzimidazolinecarbamate ethyl l-(cyan0)-3-[(p-toluoyl)carbamoyl]-A -2- benzimidazolinecarbamate ethyl 2-(propionylimino)3-(cyclohexylcarbamoyl)-lbenzimidazolinecarboxylate isopropyl 2-(propionylimino)-3-(hutylcarbarnoyl)-lbenzimidazolinecarboxylate allyl l-(hexylcarbamoyl)-2-benzimidazolecarbamate allyl 1-(methylcarbamoyl)-2-benzimidazolecarbamate allyl l-(butylcarbamoyl)-2-benzirnidazolecarbamate allyl 1- (p-toluoyl) carbamoyl] -2-benzimidazolecarbamate allyl 1-(cyclohexylcarbamoyl)-2-benzimidazolecarbamate methyl l-(cyclopropylcarbamoyl)-2-henzimidazolecarbarnate isopropyl l-(cyclopropylcarbamoyl)-2-benzimidazolecarbamate ethyl l-(cyclopropylcarbamoyl)-2-benzimidazolecarbamate methyl l-(butoxycarbonylmethyl)-3-(methylcarbamoyl)- A -2-benzimidazolinecarbamate 1-(p-chlorobenzylsulfonyl)-3-ethylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1- p-methylbenzylsulfonyl -3-butylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester l-(p-methoxybenzylsulfonyl)-3-methylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1-(p-ethylbenzylsulfonyl)-3-(2-chloroacetylcarbamoyl)- 2-henzimidazolinecarbamic acid, methyl ester 1- dodecylthiolcarbonyl -3trifiu0roacetylcarb amoyl Z-benzimidazolinecarbamic acid, methyl ester 1' allylthiolcarbonyl -3 -butylcarbamoyl-2-benzimidazolinecarbarnic acid, methyl ester 1-(propargylthiolcarbonyl)-3-methylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester l-(cyclooctylthiolcarbonyl)-3-ethylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1-(cyclohexylmethylthiolcarbonyl)-3-carbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1- (phenylthiolcarbonyl -3-butylcarbamoyl-Z-benzimidazolinecarbamic acid, methyl ester 1-(benzylthiolcarbonyl)-3-propylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1- dodecycloxythiocarbonyl -3-methylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1-(cyclopentenyloxythiocarbonyl)-3-methylcarbamoyl- 2-benzimidazolinecarbamic acid, methyl ester 1- (phenoxythioc arbonyl -3-butylcarbamoyl-2- benzimidazolinecarbamic acid, methyl ester 1-(benzyloxythiocarbonyl)-3-sec-butylcarbamoyl-2- benzimidazolinecarbamic acid, isopropyl ester l cyclohexylmethyloxythiocarbonyl -3-propylcarhamoyl- Z-benzimidazolinecarbamic acid, methyl ester l-(hexylthiolcarbonyl)-3-butylcarbamoyl-Z-benzimidazolinecarbamic acid, methyl ester EXAMPLE 10 Preparation of l-methylcarbamoyl-Z-propionamidobenzimidazole A total of 30 parts of methylisocyanate is added gradually to a stirring mixture of 94 parts of 2-propionamidobenzimidazole and 1000 parts of benzene. After the entire reaction mixture is stirred for 8 hours at room temperature, the solvent is removed under vacuum to give parts of essentially pure 1-(methylcarbamoyl)-2-propionamidobenzimidazole.

By substituting an equivalent amount or two equivalent amounts of the appropriate isocyanate for methyl isocyanate and properly substituted aminobenzimidazole for 2-propionamidobenzimidazole, the following compounds of Formula I can be made:

l-(ethylcarbamoyl -2-pr0pionamidobenzimidazole lbutylcarbamoyl -2-propionamidobenzimidazole l-(hexylcarhamoyl)-2-propionamidobenzimidazole 31 l-(p-tolylcarbamoyl)-2-propionamidobenzimidazole 1-(ethoxycarbonylmethylcarbamoyl)-2-propionamidobenzimidazole l-(cyclopropylcarbamoyl)-2-propionamidobenzimidazole l-(dodecylcarbamoyl -2-propionamidobenzimidazole 1- (piperidinocarbonyl -2-propionamidobenzimidazole 1-(cyclohexylcarbamoyl)-2-cyclopropylcarboxamidobenzimidazole 1-(butylcarbamoyl)-2-cyc1obutylcarboxamidobenzimidazole l-(phenylcarbamoyl)-2-cyclopropylcarboxamidobenzimidazole 1-(o-chlorophenylcarbamoyl)-2-cyclopropylcarboxamidobenzimidazole l-(p-bromophenylcarbamoyl)-2-cyclopropylcarboxamidobenzimidazole 1- m-fluorophenylcarbamoyl) -2-cyclopropylcarb0xamidobenzimidazole 1- 3,4-dichlorophenylcarbamoyl -2-cycl0propylearboxarnidobenzirnidazole l-(p-methoxyphenylcarbamoyl)-2-cyclopropylcarboxamidobenzimidazole 1-(p-butoxyphenylcarbamoyl)-2-cyclopropylcarboxamidobenzimidazole l-(butylcarbamoyl)-2-formamidobenzimidazole l-(methylcarbamoyl)-2-acetamidobenzimidazolc lbutylcarbamoyl -2-acetamidobenzimidazole 1- (ethylcarbamoyl -2-buty ramidobenzimidazole 1-( methylcarbamoyl)-2-butyramidobenzimidazole 1-(p-butylphenylcarbamoyl -2-propionamidobenzimidazole 1-(p-methylphenylcarbamoyl -2-propionamidobenzimidazole l-(curnylcarbamoyl)-2-propionamidobenzimidazole 1-(3,4-dimethylphenylcarbamoyl)-2-propionamidobenzimidazole 1-(rn-nitrophenylcarbamoyl)-2-propionamidobenzimidazole 1-(p-nitrophenylcarbamoyl) -2-propionamidobenzimidazole 1-(p-chlorophenylcarbamoyl)-2-propionamidobenzimidazole l-(benzylcarbamoyl) -2-propionamidobenzimidazole 1-(p-methylbenzylcarbamoyl)-2-propionamidobenzimidazole 1-(p-chlorobenzylcarbamoyl)-2-propionamidobenzimidazole 1-(3-chloro-4-methylphenylcarban1oyl)-2-propiot1- amidobenzimidazole 1-( furfurylcarbamoyl)-2-propionamidobenzimidazole 1,3-di(methylearbarnoyl)-2-formimidobenzimidazoline 1.3-di( methylcarbamoyl -2-acetamidobenzimidazoline 1.3-di (methylcarbamoyl -2-propionimidobenzimidazoline 1,3-di (butylcarbamoyl )-2-butyramidobenzimidazoline 1,3-di butylcarbamoyl -2-propionimidobenzimidazoline 1 3di(hexylcarbamoyl)-2-propionimidobenzimidazoline l,3-di(ethylcarbamoyl -2-propionimidobenzimidazoline 1-methylcarbamoyl-3-butylcarbamoyl-Z-cyclopropylcarboximidobenzimidazoline l-butylcarbamoyl-3-(p-tolylcarbamoy1)-2-propionimidobenzimidazoline EXAMPLE 11 Preparation of 1,3-di(chlorocarbonyl)-2-propionimidobenzimidazoline To a solution of 19 parts of phosgene in 300 parts of tetrahydrofuran is gradually added 18.9 parts of 2- propionamidobenzimidazole. The entire mixture is stirred under anhydrous conditions, at room temperature, for a period of 1 hour. At this point 20.2 parts triethylamine is added and the entire mixture stirred further for an additional hour at room temperature. Any solid present is discarded by filtration. The filtrate is stripped free of 32 solvent under reduced pressure and essentially pure 1,3- di(chlorocarbonyl)-2-propionimidobenzimidazoline is obtained by triturating the residue with hexane and collecting the solid by filtration.

EXAMPLE 12 Preparation of l-carbamoyl-3-chl0rocarbonyl- 2-propionimidobenzimidazoline A total of 1.7 parts of ammonia is gradually added to a stirring mixture of 14.0 parts of 1,3-dichlorocarbonyl- Z-propionimidobenzimidazoline and 300 parts of chloroform (alcohol-free). After stirring the reaction mixture for one hour, any solid present is filtered and discarded. The filtrate is washed with water, dried and the solvent is removed under reduced pressure. Essentially pure 1carbamoyl-3-chlorocarbonyl 2 propionimidobenzimidazoline is obtained by triturating the residue with hexane and collecting the product by filtration.

The following compounds can be prepared similarly by substituting equivalent amounts of the appropriate 1- chlorocarbonyl-Z-amidobenzimidazole or 1,3-(dichlorocarbonyl)-2-amidobenzimidazole or alkyl 1,3-dichlorocarbonyl-2-benzimidazolecarbamate for l-chlorocarbonyl- 2-propionamidobenzimidazole and the properly substituted amine for ammonia.

1- morpholinocarbonyl -2-cyclopropylcarboxamidobenzimidazole 1- N,N-dimethylcarbamoyl -2-propionamidobenzimidazole l- N,N-dibutylcarbamoyl -2-propionamidobenzimid azole 1- (N,N-dihexylcarbamoyl -2-propionamidobenzimidazole 1-( N-dodecyl-N-rnethylcarbamoyl -2-propionamidobenzimidazole 1- (piperidinocarbonyl -2-cyclopropylcarboxamidobenzimidazole 1- (N-rnethyl-N-phenylcarbamoyl -2-cyclopropylcarboxamidobenzirnidazole 1- N,N-dimethylcarbamoyl -2-cyclopropylca rboxamid0- benzimidazole 1- (N,N-dimethylcarbamoyl -2-cyclobutylcarboxamidobenzimidazole 1-(N,N-dibutylcarbamoyl) -2-pr0pion amidobenzirnidazole 1- (N-butyl-N-methylcarbamoyl -2-acetamidobenzimidazole 1-(N-(3-meth0xypropyl)N-methy1carbamoy1)- 2-propionamidobenzimidazole 1,3-di(carbamoyl)-2-propionimidobenzimidazoline 1,3-bis(N-methylcarbamoyl -2-propionimidobenzimidazoline 1,3 -bis (N-butylcarbamoyl -2-pr0pionimidobenzimidazoline 1, 3-bis( N,N-dirnethylcarbamoyl -2-propionin1idobenzimidazoline 1,3-bis(N-butyl-N-methylcarbamoyl) -2-propionimidobenzimidazoline 2-propionamido-l-thiolbenzimidazole carboxylic acid,

dodecyl ester 2-propionamido-1-thionobenzimidazole carboxylic acid,

benzyl ester 1-allylcarbamoyl-Z-propionamidobenzimidazole 1-propargylcarbamoyl-Z-propion amidobenzimidazole 1' 8-heptadecenylcarbamoyl -2-propionamidobenzimidazole 1- S-decynylcarbamoyl -2-cyclop ropylcarboxarnidobenzimidazole 1-( S-heptadecynylcarb amoyl -2-cyclopropylcarboxamido benzimidazole methyl 1,3 -dicarbarnoyl-2-benzim idazolecarbamate The compounds of Formula II can be prepared by reacting an aminobenzimidazolecarboxylic acid ester or amidobenzimiduzolc with one or two equivalents of a sulfenyl chloride as shown in reaction schemes (1), (2) and (3) below:

ace tone ll NaIICOs O--NII- occur. ClSCCl:

error;

l o=oso1n S'CCla O ll triethylamlne C NH-C O C Us OlS-Cl| tot rahydmlurnn N (-C 1120 H; O

iC C]; N

G =N-fi OCH:

U N f-C H2O II 0 O H g NaHCOa C'N-- OCnHg C13 acetone N NO 2 (:I -NH C H I O N O a S N C =N-t J 0 C211;

N -NH C H; II

The insoluble amine salt or sodium chloride which forms during the reaction is filtered or washed away with water and the filtrate is stripped under reduced pressure to remove the solvent and yield technical grade dior tri substituted benzimidazoles and benzimidazolines of Formula II.

The following examples are offered to illustrate the preparation of the compounds of Formula II. The amounts are given in terms of parts by weight unless otherwise specified.

EXAMPLE 13 To a mixture of 19 parts of methyl Z-benzimidazolecarbamate, parts of chloroform, 9 parts of sodium bicarbonate and 10 parts of water, a total of 19 parts of trichloromethanesulfenyl chloride is added gradually with stirring. The reaction is maintained at room temperature with external cooling. The entire reaction is stirred for an additional hour at room temperature. The solid formed is removed by filtration, washed with two volumes of water and allowed to dry. This material amounts to 27 parts of essentially pure l-(trichloromethylthio)-2- benzimidazolecarbamic acid, methyl ester.

By using equivalent amounts of properly substituted sulfenyl chlorides for the trichloromethanesulfenyl chloride and equivalent amounts of properly substituted monoor di-substituted Z-aminobenzimidazoles for the methyl-2-benzirnidazolecarbamate, the following compounds can be similarly made:

l-(methylthio)-2-benzimidazolecarbamic acid, methyl ester l-(ethylthio)-2-benzimidazolecarbamic acid, methyl ester l-(pentachloroethylthio)-2-benzimidazolecarbamic acid,

methyl ester 1- (trifiuoromethylthio -2-benzimidazolecarbamic acid,

methyl ester l-(tl ichlorumethylthio)-3-(2-ethoxycarb0nylmethyl A -2-benzimidazolinecarbamic acid, methyl ester 1- trichlychloromethylthio) -3-propionyl-2-iminobenzimidazole 3-(trifiuoromethylthi0)-1-propi0nyl-2-imin0benzimidazole 1-(2,4-dinitr0phenylthi0)-2-benzimidazolecarbamic acid,

methyl ester 1-(2,4-dinitrophenylthlo)-2-benzimidazolecarbamic acid,

ethyl ester l-(o-nitrpheny1thio)-2-benzimidazolecarbamic acid,

isopropyl ester l(2,4-dinitrophenylthi0)-2-benzimidazolecarbamic acid,

isobutyl ester l-(2,4-dinitr0phenylthi0)-2-benzimidaz0lecarbamic acid,

isopropyl ester I i-(trichloromethylthio) -2-imino-1-berlzimidazolinecarboxylic acid, methyl ester I-(trichloromethylthio)-2-benzimidazolecarbamic acid,

ethyl ester l-(triehloromethylthi0)-5-methyl-3-benzimidazolecarboxylic acid, methyl ester l-( trichloromethylthio -6-chl0ro-3-benzimidazolecarboxylic acid, ethyl ester 1(trichlor0methylthio)- -benzimidaz0lecarbamic acid,

isopropyl ester l-(hexylthio)-2-benzimidaz0lecarbamic acid, methyl ester 1- m-trifiuoromethylpheny]thio -2benzimidazolecarbamic acid, methyl ester l-methyl-3-trichloromethylthio-2-benzimidazolinecarbamic acid, methyl ester l-cyar10methyl-3-(2,2,Z-trichloroethylthio)-2-benzimidazolinecarbamic acid, methyl ester l-methoxymethyl-3-(trichloromethylthio)-2-benzimidazolinecarbamic acid, methyl ester l-methylsulfonyl-3-(trichloromethylthio)-2-benzimidazolinecarbamic acid, methyl ester 1-hexylsulf0nyl-3-(methylthio)-2-benzimidabolinecarbamic acid, methyl ester l-phenylsulfonyl-3-(trichloromethylthio)-2-benzimidazolinecarbamic acid, methyl ester l-(p-chl0rophenylsulfonyl}-3-(trichl0r0methylthi0)-2- benzimidazolinecarbamic acid, methyl ester l-(p-bromophenylsulfonyl) -3-(trichloromethylthi0 -2- benzirnidazolinecarbamic acid, methyl ester l-(p-methoxyphenylsulfonyl)-3-(trifiuor0methylthi0)- Lbenzimidazolinecarbamic acid, methyl ester l-(m-methylphenylsulfonyl) -3-(trichl0r0methylthi0 Z-benzimidaboline carbamic acid, methyl ester 1-(p-ethylphenylsulfonyl)-3-(hexylthio)-2-benzimidazolinecarbamic acid, methyl ester l-(benzylsulfonyl)-3-(trichl0r0methylthi0)-2-benzimidazolinecarbamic acid, methyl ester 1-(p-fiuorobenzylsulfonyl)-3-(o-nitr0phenylthi0)-2- benzimidazolinecarbamic acid, methyl ester 1- p-chlorobenzylsulfonyl) -3-(trichloromethylthio Z-benzimidazolinecarbamic acid, methyl ester 1- p-methoxybenzylsulfonyl) -3- trichloromethylthio 2-benzimidazolinecarbamic acid, methyl ester l-(p-methylhenzylsulfonyl -3-(trichloromethylthio) 2-benzimidazolinecarbamic acid, methyl ester l-(p-ethylbenzylsulfonyl)-3-(trichloromethylthio)-2- benzimidazolinecarbamic acid, methyl ester l-(trichloromethylthio -5-fiuor0-2-benzimidazolecarbamic acid, ethyl ester l-(trichloromethylthio -S -iod0-2-benzimidazolecarbamic acid, methyl ester l-(trichloromethylthio)-5-butoxy-Z-benzimidazolecarbamic acid, methyl ester l-(trichl0r0methylthio)-6-methoxy-2-benzimidazolecarbamic acid, methyl ester 1-(trichloromethylthiol-5-butylQ-bemimidazolccurbamic acid, methyl ester l-(methylthi0)-6-nitr0-2-benzimidaz0lccarbamic acid,

ethyl ester l-(trichloromethylthio) -3-propionyl-2-iminobenzimidazoline l- (trichloromethylthio -2- cyclopropylcarbonylamino) benzimidazole l-(trichloromethylthio)-3-(cycl0hexylcarhonyl)-2- iminobenzimidazole 2-(cyclopropylcarbonylamino)-l-(trichl0r0methylthio) benzimidazole 2-( cyclobutylcarbonylamino -l-(trichl0romethylthi0) benzimidazole l-(trichlorornethylthio)-5-nitr0-2-benzimidazolecarbamic acid, methyl ester l-(trichloromethylthio -3-(dodecylthiolcarbonyl) -2- benzimidazolinecarbamic acid, allyl ester 1-(trichloromethylthi0)-3-(allylthiolcarbonyD-Z-benzimidazolinecarbamic acid, methyl ester 1- trichloromethylthio -3- propargylthiocarboriyl) Z-benzimidazolinecarbamic acid, methyl ester 1-(cyclooctylthiolcarbonyl)-3-trichloromethylthio-2- benzimidazolinecarbamic acid, methyl ester 1-(cyclohexylmethylthiolcarbonyl)-3-trichloromethylthi0-2-benzimidazolinecarbamic acid, methyl ester 1- phenylthiolcarbonyl -3-trichloromethylthio'2-benzimidazolinecarbamic acid, methyl ester 1- (benzylthiolcarbonyl) -3-trichloromethylthio-2-benzimidazolinecarbamic acid, methyl ester 1- (phenoxythiocarbonyl -3 -trichl0r0methylthi0-2- benzimidazoline carbamic acid, methyl ester 1- hexyloxythiocarbonyl -3-trichloromethylthio-Z- benzimidazolinecarbamic acid, methyl ester l-(benzyloxythiocarbonyl)-3-trichloromethylthio-2- benzimidazolinecarbamic acid, methyl ester 1- (dodecyloyl) -3-trichloromethylthio-2-benzimidazolinecarbamic acid, methyl ester 1- (butoxyacetyl)-3-(2,4-dinitrophenylthio) -2-benzimidazolinecarbamic acid, silyl ester 1- 3-methoxypropionyl -3 -trichl0r0methylthi0-2- benzimidazolineearbamic acid, methyl ester 1-(acetoacetyl)-3-methylthio-Z-benzimidazolinecarbamic acid, methyl ester 1- (trifluoroacetyl) -3 -methylthi0-Z-benzimidazolinecarbamic acid, methyl ester l-(chlorocarbonyl)-3-methylthio-2-benzimidazolinecarbamic acid, methyl ester l-(acryoyl)-3-trich]0romethylthio-Z-benzimidazolinecarbamic acid, methyl ester I-(Z-decenoyl -3-trichlor0methylthio-2-benzimidazolinecarbamic acid, methyl ester 1- propargoyl -3 -trichl0 romethylth io-Z-benzimid azolinecarbamic acid, methyl ester 1-(2-octynoyl)-3-trichloromethylthio-2-benzimidazolinecarbamic acid, methyl ester 1-(cyclooctarioyl)-3-trichl0r0methylthi0-2-ber1zimidazolinecarbamic acid, methyl ester 1-( butoxyoxalyl -3-phenylthio-2benzimidaz0linecarbamic acid, methyl ester l-(benzoyl)-3-trichloromethylthio-Z-benzimidazolinccarbamic acid, methyl ester l-(2-nitr0benzoyl)-3-trichloromethylthio-2-benzimidazolinecarbamic acid, methyl ester l(p-chlorobenz0yl)-3-trichloromethylthio-Z-benzimidazolinecarbamic acid, methyl ester l-(2,2,2-trifluoroethylthio)-2-benzimidaz0lecarbamie acid, methyl ester l-(hexylthio)-2-benzimidazolecarbamic acid, methyl ester I-(2-chloroethylthi0) -2-benzimidazolecarbamic acid,

methyl ester l-(p-methylsulfonylphenylthi0) -2-berizimidazolecarbamic acid, methyl ester l (benzy1hiu)-2-benzimidazolccarhnmic acid, methyl ester l-(jp-butylsulfonyIphcnylJ-2-bcnzimidazulecarbamic acid,

methyl ester 37 1-(m-trifluoromethylphenyl)-2-benimidazolecarbamic acid, methyl ester 1-(trichloromethylthio)-5-bromo-2-benzimidazolecarbamic acid, methyl ester l-(pentafluoroethylthio)-2-benzimidazolecarbamic acid,

ethyl ester I-(Z-fiuoroethylthio) -2-benzimidazolecarbamic acid,

ethyl ester 2-butyramido-1-(trichloromethylthio)benzimidazole 2-acetamido-l-(trichloromethylthio)benzimidazole 2-formamido-l-(trichloromethylthio)benzimidazole 2-propionamido-l-(trichloromethylthio)benzimidazole EXAMPLE 14 A total of 38 parts of trichloromethane sultenyl chloride is added gradually with stirring to a mixture composed of 19 parts of methyl Z-benzimidazolecarbamate, 100 parts of chloroform, 18 parts of sodium bicarbonate and parts of water. External cooling is applied to the reaction to maintain the reaction at about room temperature. The entire reaction is stirred for an additional hour after the addition of trichloromethane sulfenyl chloride is completed. Essentially pure product, 1,3-bis- (trichloromethylthio) A Z-benzimidazolinecarbamic acid, methyl ester (30 parts) is obtained by filtering, water washing and drying the solid matter formed during the reaction.

By using equivalent amounts of properly substituted sulfenyl chlorides for the trichloromethane sulfenyl chloride and equivalent amounts of properly substituted monoor di-substituted Z-aminobenzimidazoles for the methyl 2- benzimidazolecarbamate the following compounds of Formula II can be similarly made.

EXAMPLE A total of parts of 2,4-dinitrophenylsulfenyl chloride is added gradually to a stirring mixture composed of 19 parts of methyl Z-benzimidazolecarbamic, 100 parts of chloroform, and 8 parts of pyridine. The reaction is stirred for an additional hour at room temperature upon completing the addition of the 2,4-dinitrophenylsulfenyl chloride. At this point, the solvent is removed under reduced pressure and the residue is washed with water and dried. The remaining solid is essentially pure l-(2,4- dinitrophenylthio)-2-benzimidazolecarbamic acid, methyl ester.

By using equivalent amounts of properly substituted sulfenyl chlorides for the 2,4-dinitrophenyl sulfenyl chloride and equivalent amounts of properly substituted monoor di-substituted 2-aminobenzimidazoles for the methyl Z-benzimidazolecarbamate, the following compounds can be similarly made.

1-(2,4-dichlorophenylthio)-2-benzimidazolecarbamic acid, methyl ester 1- p-fiuorophenylthio) -2-henzimidazolecarb amic acid, methyl ester 1-(2,4-dimethylphenylthio)-2-benzimidazolecarbamic acid, methyl ester 1- (p-methoxyphenylthio -2-benzimidazolecarbarnic acid, methyl ester 2-propioriamido-1-(2,4-dinitrophenylthio)benzimidazole Z-acetamido-l-(2,4-dinitrophenylthio)benzimidazole 38 2-butyramido-l-(2,4-dinitrophenylthio)benzimidazole 1- 2,4-dinitrophenylthio) -2-benzimidazolecarbamic acid, methyl ester 1- phenylthio -2 benzimidazolecarbamic acid, methyl ester l-(o-nitrophenylthio)-[S-fluoro]-2-benzimidazolecarbamic acid, methyl ester 1(o-nitrophenylthio)-3-(m-nitrophenylcarbamoyl)- A 2-benzimidazolinecarbamic acid, methyl ester 1-(o-methylphenylthio)-2-benzimidazolecarbamic acid, sec-butyl ester l-(3,4-dimethylphenylthio)-2.-benzimidazolecarbamic acid, methyl ester 1- (o-nitrophenylthio) -2-benzimid azolecarbamic acid, methyl ester l-( p-nitrophenylthio) -2-benzimidazolecarbamic acid, methyl ester 1-(3,4-dichlorophenylthio)-2-benzimidazolecarbamic acid, methyl ester l,3-bis(2,4-dinitrophenylthio)p -Z-benzimidazoline carbamic acid, methyl ester 1-(p-methylsulfonylphenylthio)-2-benzimidazolecarbamic acid, methyl ester 1-(p-butylsulfonylphenylthio)-2benzimidazolecarbamic acid, methyl ester l-(benzylthio)-2-benzimidazolecarbamic acid,

methyl ester 1-(o-methylbenzylthio)-2-benzimidazolecarbamic acid, methyl ester l-(p-trifluoromethylhenzylthio)-2-benzimidazolecarbamic acid, methyl ester l-(o-nitrobenzylthio)-2-benzimidazolecarbamic acid, methyl ester 1 (p-chlorobenzylthio -2-benzin1id azolecarbamic acid, methyl ester 1- (o-fiuorobenzylthio -2-benzimidazolecarbamic acid, methyl ester 1-(o-methoxybenzylthio)-Z-benzimidazolecarbamic acid, methyl ester 1-(p-ethylsulfonylbenzylthio)-2-benzimidazolecarbamic acid, methyl ester EXAMPLE 16 A total of 19 parts of trichloromethanesulfenyl chloride is added gradually to a stirring mixture composed of 24.8 parts of 1-methoxycarbonyl-2-benzimidazolecarbamic acid, methyl ester, parts of chloroform, and 11 parts of triethylamine. After stirring the reaction for an additional two hours after completing the above addition, the solvent is removed under reduced pressure with a minimum of heat. The residue is washed with Water, dried and is essentially pure l-methoxycarbonyl-3-(trichloromethylthio)-2-benzimidazolecarbamic acid, methyl ester.

By using equivalent amounts of properly substituted sulfenyl chlorides for the trichloromethane sulfenyl chloride and equivalent amounts of properly substituted monoor di-substituted Z-aminobenzimidazoles for the 1- methoxycarbonyl-Z-benzimidazolecarbamic acid, methyl ester, the following compounds of Formula II can be similarly made.

ltrichloromethylthio) -3- 3 -chloropropylcarbamoyl A -2-benzimidazolinecarbamic acid, methyl ester l- (trichloromethylthio -3-( dimethylcarbamoyl -A -2- benzimidazolinecarbamic acid, methyl ester 1- trichloromethylthio) -3-(N-methyl-N- 3-methoxypropyl) -carbamoyl -A -2-cyclopropylcarboximinobenzimidazoline l- (trichloromethylthio) -3-( 2-chloroethylcarbamoyl) A -2-benzimidazolinecarbamic acid, ethyl ester ltrichloromethylthio) -3-( N,N-dibutylcarbamoyl -A Z-benzimidazolinecarbamic acid, methyl ester lp-butoxybenzylthio -3- methoxyacetyl) -A -2- benzimidazolinecarbamic acid. methyl ester 39 l-(trichloromethylthio)-3-(cyanoacetyl)-A -2-benzimidazolinecarbamic acid, methyl ester 1- trichloromethylthio -3- hydroxyacetyl -A -2-benzimidazolinecarbamic acid, methyl ester l-(trichloromethylthio)-3-(ethoxycarbonylmethylcarbamoyl)-A -2-benzimidazolinecarbamic acid, methyl ester 1- trifiuoromethylthio -3 p-rnethoxyphenylcarbamoyl A -Z-benzimidazolinecarbamic acid, methyl ester 1- (trifiuoromethylthio -3- 3,4-dichlorophenylcarhamoyl)-A 2-benzimidazolinecarbamic acid, methyl ester 1-( trichloromethylthio) -2-(methoxycarbonylimino) -3- thionobenzimidazolinecarboxylic acid, methyl ester l-(trichloromethylthio)-2-(methoxycarbonylimino)-3- dithiobenzimidazolinecarboxylic acid, methyl ester l-(methylthio)-2-(butoxycarbonylimino)-3-thiobenzimidazolinecarboxylic acid, hexyl ester 1-(trichloromethylthio)-Z-(methoxycarbonylimino)-3- thionobenzimidazolinecarboxylic acid, Z-cyanoethyl ester l-(trichloromethylthio)-2-(methoxycarbonylimino)-3- thionohenzimidazolinecarboxylic acid, 2-chloroethyl ester l-(trichloromethylthio)-2-(ethoxycarbonylimino)-3- thionobenzimidazolinecarboxylic acid, S-methoxypropyl ester l-(trichloromethylthio)-2-(methoxycarbonylimino)-3- thiolbenzimidazolinecarboxylic acid, isopropyl ester l( trichloromethylthio -3-cyano-A -2-benzimidazolinecarbamic acid, methyl ester 1-(trichloromethylthio)-3-formyl-A -2-benzimidazolinecarbamic acid, ethyl ester 1-(2,4-dinitrophenylthio)-3-cyano-A -2-benzimidazolinecarbamic acid, methyl ester l-( trichloromethylthio) -3-( methylca rbamoy] A -2- benzimidazolinecarbamic acid, methyl ester l-(trifluoromethylthio)-3-pr0pionyl-A -2-benzimidazolinecarbamic acid, methyl ester 1- trifluoromethylthio -3 -acetyl-A -Z-benzimidazolinecarbamic acid methyl ester 1- trichloromethylthio -3-propionyl-A -2-benzimidaz0- linecarbamic acid, methyl ester l-(trichloromethylthio) 3-propi0nyl-A -2-pr0pi0nimidobenzimidazoline l-(trichloromethylthio) -3-cyclopropylcarbOnyl-A -Z- benzimidazolinecarbamic acid, methyl ester l-(dimethoxyphosphoryl)-3-trichloromethylthi0-2-benzimidazolinecarbamic acid, methyl ester l-(diethoxyphosphoryl)-3-trichloromethylthio-Z-benzirnidazolinecarbamic acid, methyl ester 1-(dimethoxythiophosphoryl)-3-trichloromethylthio-2- henzimidazolinecarbamic acid, methyl ester 1- trichloromethylthio -3-(dodecylcarbam0yl A -2- benzimidazolinecarbamic acid, methyl ester l-(trichloromethylthio)-3-(phenylcarbamoyl)-A -2- benzimidazolinecarbamic acid, methyl ester l-(trichloromethylthio)-3-(cyclohexylcarbamoyl)-A -2- benzimidazolinecarbamic acid, methyl ester l-(trichloromethylthio)-3-(p-tolylcarbamoyl)A -2- benzimidazolinecarbamic acid, methyl ester l-(trichloromethylthio)-3-(butylcarbamoyl)A -2- benzimidazolinecarbamic acid, methyl ester l-( trichloromethylthio) -3-(hexylcarhamoyl)-A -2- benzimidazo]inecarbamic acid, methyl ester l-(trichloromethylthio -3-(henzylcarbam0yl -A -2- benzimidazolinecarbamic acid, methyl ester l-( trichloromethylthio)-3- (o-chlorophenylcarbamoyl) A -Z-benzimidazolinecarbamic acid, methyl ester 1-(trichloromethylthio)-3-(p-butylphenylcarbamoyl)- N- -2-benzimidazolinecarbamic acid, methyl ester l-(trichloromethylthio)-3-(methoxycarhonyl)-A -2- benzimidazolirtecarbamic acid, methyl ester l-(2,4-dinitrophenylthio)-3-(methoxycarbonyl)-A -2- benzimidazolinecarbamic acid, methyl ester l-(trichloromethylthio)-3(2-chloroethoxycarbonyl) d -l-benzimidazolinecarbamic acid, methyl ester l-(trichloron1ethylthio 3- amyloxycarbonyl l -A -2- benzimidazolinecarbamic acid, methyl ester 1-( trichloromethylthio -3- 2cyar1oethoxycarbonyl) A -2-benzimidazolinecarbamic acid, isopropyl ester l-(trichloromethylthio)-3-(Z-hydroxypropoxycarbonyU- A -l-benzimidazolinecarbamic acid, methyl ester methyl 1-al1yl-3-(trichloromethylthio)-A -2- benzimidazolinecarbamate methyl I-(Z-butenyl)-3-(trichloromethylthio)A -2- benzimidazolinecarbamate methyl 1-propargyl-3-(trichloromethylthio)A -2- benzimidazolinecarbamate allyl l-(trichloromethylthio)-2-benzimidazolecarbamate 1- methoxyoxalyl) -3 (trichloromethylthio -A -2- benzimidazolinecarbamic acid, methyl ester l-(ethoxyoxalyl)-3-(trichloromethylthio)-A -2- benzimidazolinecarbamic acid, methyl ester l-(benzyloxycarbonyl)-3-(trichloromethylthio)-2- (methoxycarbonylimino)benzimidazoline l-(phenoxycarbonyl)-3-(trichloromethylithio)-2- (isopropoxycarbonylimino benzimidazoline l(octadecylcarbamoyl)-3-(trichloromethylthio)-2- methoxycarbonylimino benzimidazoline l-(allylcathamoyl)-3-(trichloromethylthio)-2- (methoxycarbonylimino)benzimidazoline l-( 2-dodecenoylca rbamoyl -3-(trichloromethylthio) -2- (methoxycarbonylimino)benzimidazoline 1(stearoloylcarbamoyl)3-(methylthio)-2- (methoxycarbonylimino)benzimidazoline 1-(undecoloylcarbamoyl)-3-(trichloromethylthio)-2- (methoxycarbonylimino)benzimidazoline l-(tetroloylcarbamoyl)-3-(2,4-trichloromethylthio)-2- methoxycarbonylimino)benzimidazoline l-(tetroloylcarhamoyl)-3-(2,4-dinitr0phenylthi0)-2- (methoxycarbonylimino)benzimidazoline 1-(propargylcarbamoyl)-3-(2,4-dinitrophenylthio)-2- (methoxycarbonylimino)benzimidazolirte l- 8-heptadecenylcarhamoyl) -3-(trichloromethylthio) -2- (methoxycarhonylimino) benzimidazoline methyl l-(3-hexenylcarbam0yl)-3-(trichloromethyltl1io)- A -2ber1zimidazolinecarbamate methyl l-(acetylcarbamoyl)-3-(trichloromethylthio)- A -2-benzimidazolinecarbamate ethyl 1-(stearoylcarbamoyl)-3-(trichloromethylthio)- A -2-benzimidazolinecarbamate isopropyl l-(acryloylcarhamoyl)-3-(trichl0r0methylthi0)- A -2-benzimidazolinecarbarnate isopropyl l-(propioloylcarbamoyl)-3-(methylthio) A -2-benzimidazolinecarbamate methyl 1-(trichloroacetylcarbamoyl)-3-(methylthio)- A -2-benzimidazolinecarbamate methyl 1- (elaidoylcarbamoyl) -3- (trich10romethylthi0)- A -2-benzimidazolinecarbamate methyl 1-(trifluoroacetylcarbamoyl)-3- (trichloromethylthio)A -Z-benZimidazolinecarbamate isopropyl 1-(p-chlorohenzylcarbamoyl)-3- (trichloromethylthio)-A -Z-benzimidazolinecarhamate isopropyl 1-(o-nitrobenzylcarbamoyl)-3- (trichloromethylthio)-A -2-benzimidazolinecarbamate methyl l-(hexylthio)-2-benzimidazolecarhamate allyl 1-( trichloromethylthio) -2-benzimidazolecarbamate N ll 

